Insecticidal carbamoyl sulfides

ABSTRACT

4-Oxo-2,5-cyclohexadien-1-ylideneaminooxy derivatives, such as N-[[[N-[[N-[3,5-bis(1,1-dimethylethyl)-4-oxo-2,5-cyclohexadien-1-ylidenaminooxycarbonyl]-N-methylaminothio]]-N-methylaminocarbonyloxy]]]ethanimidothioic acid, methyl ester, useful for control of insects.

BACKGROUND OF THE INVENTION

This invention relates to carbamoyl sulfides useful as insecticides.

Belgian Pat. No. 848,911 discloses asymmetric insecticidal N-substituted bis-carbamoyl sulfides of the formula ##STR1## where R, R', R₁ and R₂ are as defined in the publication.

Belgian Pat. No. 848,912 discloses symmetrical insecticidal N-substituted bis-carbamoyl sulfides of the formula ##STR2## where R and R' are as defined in the publication.

Belgian Pat. No. 848,913 discloses insecticidal oxime thiobis-carbamates of the formula ##STR3## where R, R', R₁ and R₂ are as defined in the patent.

The compounds taught in these patents are active insecticides. Nevertheless, the need of new, highly active insecticides still exist. The use of active insecticides for the protection of beneficial crops is one way to resolve the world-wide food shortage.

The novel 4-oxo-2,5-cyclohexadien-1-ylideneaminooxy derivatives of this invention are highly active insecticides especially on Lepidoptera species such as tobacco budworm and southern armyworm. These compounds provide long residual activity with little or no redding of cotton.

SUMMARY OF THE INVENTION

This invention relates to novel 4-oxo-2,5-cyclohexadien-1-ylideneaminooxy derivatives of Formula I, to novel 2-oxo-3,5-cyclohexadien-1-yl-ideneaminooxy derivatives of Formula IX, to agricultural compositions containing them and to their method of use as insecticides. ##STR4##

R¹, R², R³, and R⁴ are independently H, F, Cl, Br, NO₂, CN, CF₃, C₁ -C₁₂ alkyl, C₁ -C₄ alkoxy, or COR⁵ ;

R⁵ is OR⁶ or NR⁷ R⁸ ;

R⁶ is C₁ -C₄ alkyl;

R⁷ is C₁ -C₄ alkyl or methoxy;

R⁸ is C₁ -C₄ alkyl;

R⁹ and R¹⁰ are independently methyl or ethyl; or

R¹ and R² are taken together to form

    --CH═CH--CH═CH--;

provided that:

(1) The total of R⁹ and R¹⁰ is not greater than three carbon atoms;

(2) Only one of R¹, R², R³ and R⁴ can be CN, NO₂, COR⁵, or CF₃ ;

(3) If R² and R⁴ are both alkyl, then R² and R⁴ are independently CH₃ or CH₂ CH₃ ;

(4) If any two of R¹, R², R³, and R⁴ are independently halogen or alkoxy, then the other two are independently hydrogen or CH₃ ;

(5) The total number of carbons R¹ to R⁴ is not greater than 26;

(6) If R¹ and R² are both alkyl, then R² must be CH₃ or CH₂ CH₃ ;

(7) If R³ and R⁴ are both alkyl, then R⁴ must be CH₃ or CH₂ CH₃.

The compounds of formula IX are of the formula ##STR5## wherein

R is as previously defined including definitions of R⁹ and R¹⁰ ;

R¹¹, R¹², R¹³ and R¹⁴ are independently, H, C₁ -C₁₂ alkyl, C₁ -C₄ alkoxy, Cl or Br; or

either R¹¹ and R¹² or R¹³ and R¹⁴ are taken together to form --CH═CH--CH═CH--;

provided that

(1) the total of R⁹ and R¹⁰ is not greater than three carbon atoms;

(2) if three or more of R¹¹, R¹², R¹³ and R¹⁴ are other than H, then any of R¹¹, R¹², R¹³ and R¹⁴ which is not H, is selected from CH₃ or Cl, except that if R¹¹ and R¹² or R¹³ and R¹⁴ form the bridge --CH═CH--CH═CH--, then the remaining R¹¹ to R¹⁴ groups are chosen from all definitions of R¹¹ to R¹⁴ ;

(3) if any of R¹¹, R¹², R¹³ and R¹⁴ is secondary alkyl, tertiary alkyl or tertiary alkoxy, the adjacent group which is at least one of R¹¹, R¹², R¹³ or R¹⁴ must be selected from H, CH₃ or CH₂ CH₃ ;

(4) the total number of carbons of R¹¹ to R¹⁴ is not greater than 16.

Also, this invention relates to novel intermediates of the formulae ##STR6## where R¹, R², R³, R⁴, R¹¹,R¹², R¹³ and R¹⁴ are as previously defined.

PREFERRED COMPOUNDS

Preferred for their ease of synthesis are those compounds of Formulae I and IX where R¹ and R⁴ are independently H, Cl, F, C₁ -C₅ alkyl, C₁ -C₃ alkoxy, or CO₂ R₆ where R⁶ is C₁ -C₄ alkyl; R¹¹ to R¹⁴ are independently H, Cl, C₁ -C₅ alkyl and C₁ -C₃ alkoxy.

More preferred for higher insecticidal activity are those compounds of the preferred scope wherein R⁹ and R¹⁰ are CH₃.

Most preferred for even higher insecticidal activity are those compounds of the more preferred scope wherein R² and R⁴ are H and R¹ and R³ are independently C₁ -C₅ alkyl; R¹² and R¹⁴ are H and R¹¹ and R¹³ are independently C₁ -C₅ alkyl.

Specifically preferred for high insecticidal activity are the compounds:

N-[[[N-[N-[3,5-bis(1,1-dimethylethyl)-4-oxo-2,5-cyclohexadien-1-ylideneaminooxycarbonyl]-N-methylaminothio]]-N-methylaminocarbonyloxy]]-ethanimidothioic acid, methyl ester

N-[N-[N-(3,5-dimethyl-4-oxo-2,5-cyclohexadien-1-ylideneaminooxycarbonyl)-N-methylaminothio]-N-methylaminocarbonyloxy]ethanimidothioic acid, methyl ester

N-[N-methyl-N-[N-methyl-N-[2-methyl-5-(1-methylethyl)-4-oxo-2,5-cyclohexadien-1-ylideneaminooxycarbonyl]-aminothio]aminocarbonyloxy]-ethanimidothioic acid, methyl ester

N-[N-[N-[3,5-bis(1-methylpropyl)-4-oxo-2,5-cyclohexadien-1-ylideneaminooxycarbonyl]-N-methylaminothio]-N-methylaminocarbonyloxy]-ethanimidothioic acid, methyl ester

N-[N-[N-[3,5-bis(1-methylethyl)-4-oxo-2,5-cyclohexadien-1-ylideneaminooxycarbonyl]-N-methylaminothio]-N-methylcarbonyloxy]ethanimidothioic acid, methyl ester

methyl N-[N-[N-[[3,5-bis(1,1-dimethylethyl)-6-oxo-2,4-cyclohexadien-1-ylidene]aminoxycarbonyl]-N-methylaminothio]-N-methylaminocarbonyloxy]ethanimidothioate

methyl N-[N-[N-[(3-dodecyl-1,4-dihydro-4-oxo-1-naphthaleneidene)aminooxycarbonyl]-N-methylaminothio]-N-methylaminocarbonyloxy]ethanimidothioate

methyl N-[N-[N-[(1,2-dihydro-1-oxo-2-naphthalenylidene)aminooxycarbonyl]-N-methylaminothio]-N-methylaminocarbonyloxy]ethanimidothioate

methyl N-[N-[N-[(1,4-dihydro-3-methyl-4-oxo-1-naphthalenylidene)aminooxycarbonyl]-N-methylaminothio]-N-methylaminocarbonyloxy]-ethanimidothioate

SYNTHESIS

Novel compounds of this invention can be prepared by the reaction of the carbamoyl fluoride of Formula IV and a nitrosophenol of Formula V as shown in Scheme I: ##STR7## where R, R¹, R², R³ and R⁴ are as defined in the previous section. An acid scaverger is normally employed, and either an organic base such as triethylamine, pyridine, dialkylaniline or an inorganic base such as potassium hydroxide or potassium carbonate can be used. The reaction temperature can be varied from -20° to 80° C. in a period of 10 minutes to 24 hours. An aprotic solvent such as ether, toluene, methylene chloride, etc. can be chosen as the reaction medium. It is preferred that the reaction be conducted in diethyl ether or toluene at ambient temperature for 30 minutes to 4 hours in the presence of triethylamine.

Compounds of Formula I can also be prepared by the reaction of Compound IV and an anion of the nitrosophenol (V), generated by a base such as sodium hydride, in an aprotic solvent, preferably in dry tetrahydrofuran at -20° to 30° C.

An alternative way for preparing compounds of Formula I can be illustrated as shown in Scheme II. ##STR8## wherein R, R¹, R², R³ and R⁴ were defined in the previous section.

The reaction of the nitrosophenol (V) and VII can be carried out in an aprotic solvent such as diethyl ether, tetrahydrofuran, methylene chloride, toluene or a mixed solvent at -20° to 30° C. for 30 minutes to 5 hours. An organic tertiary amine such as triethylamine is preferred to be the acid acceptor. Under the similar reaction conditions, compounds of Formula I can be prepared by the reaction of VIII and RH. However, either an organic tertiary amine or an inorganic hydroxide or carbonate can be chosen as acid acceptor.

Novel compounds of Formula IX can be obtained either from the reaction of an o-nitrosophenol and the carbamoyl fluoride of Formula IV ##STR9## or from the reaction of compounds of Formula X and RH under similar conditions under which compounds of Formula I were prepared. Compounds of Formula X can be synthesized by the reaction of an o-nitrosophenol and compound VII as described for the preparation of compound VIII. ##STR10##

The preparation of o-nitrosophenols has been described in the literature [cf., Acta Chim. Acad. Sci. Hung., 98, 327 (1978)] and references cited therein.

The nitrosophenol (V) exhibits the character of a quinone monoxime. The tautomerization has been well documented [J. Org. Chem., 21, 1201 (1956)]. ##STR11##

The carbamoyl fluorides of Formula IV and VII can be prepared by the methods taught in DT No. 2654282.

In the above reaction procedures, pressure is not critical, but for convenience, atmospheric pressure is preferred.

The preparation of compounds in this invention can be more clearly demonstrated by the following examples. Unless otherwise stated, all temperatures are in degrees Centigrade and parts are by weight.

EXAMPLE 1 N-[[[N-[[3,5-bis(1,1-dimethylethyl)-4-oxo-2,5-cyclohexadien-1-ylideneaminooxycarbonyl]-N-methylaminothio]]-N-methylaminocarbonyloxy]]-ethanimidothioic acid, methyl ester

A solution of 1.2 g of triethylamine in 10 ml of dry ether was added dropwise to a mixture of 2.4 g of 2,6-di-t-butyl-4-nitrosophenol and 2.7 g of N-[[[N-[[N-fluorocarbonyl-N-methylaminothio]]-N-methylaminocarbonyloxy]]]ethanimidothioic acid methyl ester suspended in 40 ml of dry ether at a temperature below 25°. The mixture was stirred at room temperature for 50 minutes. Then, water and hexane were added to the mixture. The product was collected by filtration, washed with water, hexane, and air-dried to give 4.1 g of N-[[[N-[[3,5-bis-(1,1-dimethylethyl)-4-oxo-2,5-cyclohexadien-1-yli-deneaminooxycarbonyl]-N-methylaminothio]]-N-methylaminocarbonyloxy]]ethanimidothioic acid methyl ester, m.p. 160°-161.6°.

EXAMPLE 2 [[[N-[[3,5-bis[1,1-dimethylethyl]-4-oxo-2,5-cyclohexadien-1-ylideneaminooxycarbonyl]]-N-methylaminothio]]]methylcarbamic fluoride

A solution of 2.1 g of triethylamine in 10 ml of dry ether was added dropwise to a suspension of 4.7 g of 2,6-di-tert-butyl-4-nitrosophenol and 3.8 g of N,N'-thiobis[N-methylcarbamic fluoride] in a mixture of 60 ml of dry methylene chloride and 20 ml of ether at 0° to 5°. A clear solution was obtained after the addition. The mixture was stirred on an ice bath for 3 hours and hexane was added. The mixture was washed with water twice, dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated to give an oil which was crystallized from cold hexane to yield 4.1 g of [[[N-[[3,5-bis[1,1-dimethylethyl]-4-oxo-2,5-cyclohexadien-1-ylideneaminooxycarbonyl]]-N-methylaminothio]]]methylcarbamic fluoride, m.p. 109.5°-113°.

EXAMPLE 3 N-[[[[N-[[[N-[[3,5-bis[1,1-dimethylethyl]-4-oxo-2,5-cyclohexadien-1-ylideneaminooxycarbonyl]]N-methylaminothio]]]-N-methylaminocarbonyloxy]]]]-2-dimethylamino]-2-oxo-ethanimidothioic acid, methyl ester

A mixture of 3.2 g of [[[N-[[3,5-bis[1,1-dimethylethyl]-4-oxo-2,5-cyclohexadien-1-ylideneaminooxycarbonyl]]-N-methylaminothio]]]methylcarbamic fluoride, 1.4 g of N,N-dimethyl-2-hydroximino-2-methylthioacetamide and 1 g of triethylamine in 30 ml of dry ether was stirred at room temperature for 2 hours. Hexane and water were added. The organic phase was removed under vacuum. The crude product was obtained by filtration and recrystallized from hexane-ether mixture to give 3.4 g of N-[[[[N-[[[N-[[3,5-bis[1,1-dimethylethyl]-4-oxo-2,5-cyclohexadien-1-ylideneaminooxycarbonyl]]-N-methylaminothio]]]-N-methylaminocarbonyloxy]]]]-2-dimethylamino]-2-oxo-ethanimidothioic acid methyl ester, m.p. 155°-159°.

The novel compounds of this invention can be prepared by the methods set forth including but not restricted by the following examples.

                                      TABLE 1                                      __________________________________________________________________________      ##STR12##                                                                     R.sup.1 R.sup.2 R.sup.3  R.sup.4 R.sup.9                                                                           R.sup.10                                                                          melting point °C.                __________________________________________________________________________     CH.sub.3                                                                               H       CH.sub.3 H       CH.sub.3                                                                          CH.sub.3                                                                          175.5-178                               i-Pr    H       H        CH.sub.3                                                                               CH.sub.3                                                                          CH.sub.3                                                                          90-99                                   sec-Bu  H       sec-Bu   H       CH.sub.3                                                                          CH.sub.3                                                                          103-106                                 i-Pr    H       i-Pr     H       CH.sub.3                                                                          CH.sub.3                                                                          120.5-121.5                             H       t-Bu    t-Bu     H       CH.sub.3                                                                          CH.sub.3                                                                          178-179.5                               Cl      H       Cl       H       CH.sub.3                                                                          CH.sub.3                                                                          140-142(dec.)                           H       H       H        H       CH.sub.3                                                                          CH.sub.3                                                                          174-177(dec.)                           H       Cl      H        Cl      CH.sub.3                                                                          CH.sub.3                                   H       Cl      Cl       H       CH.sub.3                                                                          CH.sub.3                                   F       H       F        H       CH.sub.3                                                                          CH.sub.3                                   H       F       H        H       CH.sub.3                                                                          CH.sub. 3                                  CH.sub.3                                                                               H       H        F       CH.sub.3                                                                          CH.sub.3                                   Br      H       H        Br      CH.sub.3                                                                          CH.sub.3                                   H       Br      H        H       CH.sub.3                                                                          CH.sub.3                                   H       H       Br       H       CH.sub.3                                                                          CH.sub.3                                   CH.sub.3                                                                               CH.sub.3                                                                               CH.sub.3 CH.sub.3                                                                               CH.sub.3                                                                          CH.sub.3                                                                          162.5-166.5                             H       Et      H        Et      CH.sub.3                                                                          CH.sub.3                                   H       CH.sub.3                                                                               CH.sub.3 H       CH.sub.3                                                                          CH.sub.3                                                                          131.5-133.5                             CH.sub.3                                                                               NO.sub.2                                                                               H        H       CH.sub.3                                                                          CH.sub.3                                   H       H       NO.sub.2 CH.sub.3                                                                               CH.sub.3                                                                          CH.sub.3                                   NO.sub.2                                                                               H       H        CH.sub.3                                                                               CH.sub.3                                                                          CH.sub.3                                   H       H       H        NO.sub.2                                                                               CH.sub.3                                                                          CH.sub.3                                   CN      H       H        H       CH.sub.3                                                                          CH.sub.3                                   H       CN      H        H       CH.sub.3                                                                          CH.sub.3                                   t-Bu    H       t-Bu     CN      CH.sub.3                                                                          CH.sub.3                                   CH.sub.3                                                                               H       CN       CH.sub.3                                                                               CH.sub.3                                                                          CH.sub.3                                   CF.sub.3                                                                               H       H        H       CH.sub.3                                                                          CH.sub.3                                   H       CF.sub.3                                                                               H        H       CH.sub.3                                                                          CH.sub.3                                   CHCHCHCH        n-C.sub.12 H.sub.25                                                                     H       CH.sub.3                                                                          CH.sub.3                                                                          87-88.5                                 CHCHCHCH        CH.sub.3 H       CH.sub.3                                                                          CH.sub.3                                                                          156-159(dec.)                           Cl      H       H        CF.sub.3                                                                               CH.sub.3                                                                          CH.sub.3                                   H       Cl      CF.sub.3 H       CH.sub.3                                                                          CH.sub.3                                   CH.sub.3 O                                                                             H       CH.sub.3 O                                                                              H       CH.sub.3                                                                          CH.sub.3                                   n-BuO   H       n-BuO    H       CH.sub.3                                                                          CH.sub.3                                   H       CH.sub.3 O                                                                             CH.sub.3 O                                                                              H       CH.sub.3                                                                          CH.sub.3                                   H       n-BuO   n-BuO    H       CH.sub.3                                                                          CH.sub.3                                   H       H       H        CH.sub.3 O                                                                             CH.sub.3                                                                          CH.sub.3                                   H       H       H        n-BuO   CH.sub.3                                                                          CH.sub.3                                   n-C.sub.12 H.sub.25                                                                    H       H        H       CH.sub.3                                                                          CH.sub.3                                   H       n-C.sub.12 H.sub.25                                                                    H        H       CH.sub.3                                                                          CH.sub.3                                   H       CH.sub.3                                                                               n-C.sub.12 H.sub.25                                                                     H       CH.sub.3                                                                          CH.sub.3                                   CH.sub.3                                                                               H       H        n-C.sub.12 H.sub.25                                                                    CH.sub.3                                                                          CH.sub.3                                   CH.sub.3                                                                               H       CO.sub.2 CH.sub.3                                                                       H       CH.sub.3                                                                          CH.sub.3                                   CH.sub.3                                                                               H       CO.sub.2 t-Bu                                                                           H       CH.sub.3                                                                          CH.sub.3                                   CH.sub.3                                                                               H       CONMe.sub.2                                                                             H       CH.sub.3                                                                          CH.sub.3                                   CH.sub.3                                                                               H       CON(n-Bu).sub.2                                                                         H       CH.sub.3                                                                          CH.sub.3                                   CH.sub.3                                                                               H       CON(OCH.sub.3)CH.sub.3                                                                  H       CH.sub.3                                                                          CH.sub.3                                   CO.sub.2 CH.sub.3                                                                      H       Et       H       CH.sub.3                                                                          CH.sub.3                                   CO.sub.2 n-Bu                                                                          H       Et       H       CH.sub.3                                                                          CH.sub.3                                   CONMe.sub.2                                                                            H       Et       H       CH.sub.3                                                                          CH.sub.3                                   CON(n-Bu).sub.2                                                                        H       Et       H       CH.sub. 3                                                                         CH.sub.3                                   CON(OMe)Me                                                                             H       Et       H       CH.sub.3                                                                          CH.sub.3                                   H       CO.sub.2 CH.sub.3                                                                      H        H       CH.sub.3                                                                          CH.sub.3                                   H       CO.sub.2 n-Bu                                                                          H        H       CH.sub.3                                                                          CH.sub.3                                   H       CONMe.sub.2                                                                            H        H       CH.sub.3                                                                          CH.sub.3                                   H       CON(n-Bu).sub.2                                                                        H        H       CH.sub.3                                                                          CH.sub.3                                   H       CON(OMe)Me                                                                             H        H       CH.sub.3                                                                          CH.sub.3                                   Cl      H       H        CO.sub.2 CH.sub.3                                                                      CH.sub.3                                                                          CH.sub.3                                   Cl      H       H        CO.sub.2 n-Bu                                                                          CH.sub.3                                                                          CH.sub.3                                   Cl      H       H        CONMe.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                   Cl      H       H        CON(n-Bu).sub.2                                                                        CH.sub.3                                                                          CH.sub.3                                   H       H       H        CO(OMe)Me                                                                              CH.sub.3                                                                          CH.sub.3                                   t-Bu    H       t-Bu     H       Et CH.sub.3                                   t-Bu    H       CH.sub.3 H       CH.sub.3                                                                          CH.sub.3                                                                          136-139                                 t-Bu    H       t-Bu     H       CH.sub.3                                                                          Et                                         sec-Bu  H       sec-Bu   H       CH.sub.3                                                                          Et                                         H       t-Bu    t-Bu     H       CH.sub.3                                                                          Et                                         CH.sub.3                                                                               H       CH.sub.3 H       CH.sub.3                                                                          Et                                         EtC(CH.sub.3).sub.2                                                                    H       EtC(CH.sub.3).sub.2                                                                     H       CH.sub.3                                                                          CH.sub.3                                   t-Bu    H       H        CH.sub.3                                                                               CH.sub.3                                                                          CH.sub.3                                                                          106-110(dec.)                           __________________________________________________________________________

                  TABLE 2                                                          ______________________________________                                          ##STR13##                                                                                                          melting                                   R.sup.1  R.sup.2                                                                               R.sup.3    R.sup.4                                                                             R.sup.10                                                                            point °C.                          ______________________________________                                         t-Bu     H      H          H    CH.sub.3                                       sec-Bu   H      sec-Bu     H    CH.sub.3                                       t-Bu     H      t-Bu       H    Et                                             H        CH.sub.3                                                                              i-Pr       H    CH.sub.3                                       CH.sub.3 H      CH.sub.3   H    CH.sub.3                                       EtC(CH.sub.3).sub.2                                                                     H      EtC(CH.sub.3).sub.2                                                                       H    CH.sub.3                                       CH.sub.3 CH.sub.3                                                                              CH.sub.3   CH.sub.3                                                                            CH.sub.3                                       H        t-Bu   t-Bu       H    CH.sub.3                                       Cl       H      Cl         H    CH.sub.3                                       i-Pr     H      i-Pr       H    CH.sub.3                                       ______________________________________                                    

                  TABLE 3                                                          ______________________________________                                          ##STR14##                                                                     R.sup.1  R.sup.2 R.sup.3    R.sup.4                                                                              melting point °C.                     ______________________________________                                         t-Bu     H       t-Bu       H                                                  H        t-Bu    t-Bu       H                                                  EtC(CH.sub.3).sub.2                                                                     H       EtC(CH.sub.3).sub.2                                                                       H                                                  CH.sub.3 H       CH.sub.3   H                                                  CH.sub.3 CH.sub.3                                                                               CH.sub.3   CH.sub.3                                           sec-Bu   H       sec-Bu     H                                                  H        H       t-Bu       H                                                  i-Pr     H       i-Pr       H                                                  H        CH.sub.3                                                                               i-Pr       H                                                  ______________________________________                                    

                  TABLE 4                                                          ______________________________________                                          ##STR15##                                                                     R.sup.1  R.sup.2 R.sup.3    R.sup.4                                                                              melting point °C.                     ______________________________________                                         t-Bu     H       t-Bu       H     oil                                          EtC(CH.sub.3).sub.2                                                                     H       EtC(CH.sub.3).sub.2                                                                       H                                                  sec-Bu   H       sec-Bu     H                                                  CH.sub.3 H       CH.sub.3   H                                                  i-Pr     H       i-Pr       H                                                  CH.sub.3 CH.sub.3                                                                               CH.sub.3   CH.sub.3                                           t-Bu     H       H          t-Bu                                               i-Pr     H       H          CH.sub.3                                           ______________________________________                                    

                                      TABLE 5                                      __________________________________________________________________________      ##STR16##                                                                     R.sup.11                                                                              R.sup.12                                                                             R.sup.13                                                                              R.sup.14                                                                             R.sup.9                                                                           R.sup.10                                                                          melting point °C.                       __________________________________________________________________________     t-Bu   H     t-Bu   H     CH.sub.3                                                                          CH.sub.3                                                                          142-145                                        t-Bu   H     H      t-Bu  CH.sub.3                                                                          CH.sub.3                                          H      H     Cl     H     CH.sub.3                                                                          CH.sub.3                                          H      Br    Br     H     CH.sub.3                                                                          CH.sub.3                                          Cl     H     Cl     H     CH.sub.3                                                                          CH.sub.3                                          Br     H     Br     H     CH.sub.3                                                                          CH.sub.3                                          H      Cl    Cl     H     CH.sub.3                                                                          CH.sub.3                                          CH.sub.3                                                                              Cl    CH.sub.3                                                                              Cl    CH.sub.3                                                                          CH.sub.3                                          CH.sub.3                                                                              CH.sub.3                                                                             CH.sub.3                                                                              CH.sub.3                                                                             CH.sub.3                                                                          CH.sub.3                                          CH.sub.3                                                                              H     CH.sub.3                                                                              Br    CH.sub.3                                                                          CH.sub.3                                          n-C.sub.12 H.sub.25                                                                   H     H      H     CH.sub.3                                                                          CH.sub.3                                          H      H     n-C.sub. 12 H.sub.25                                                                  H     CH.sub.3                                                                          CH.sub.3                                          CH.sub.3                                                                              H     H      n-C.sub.12 H.sub.25                                                                  CH.sub.3                                                                          CH.sub.3                                          CH.sub.3 O                                                                            H     CH.sub.3                                                                              H     CH.sub.3                                                                          CH.sub.3                                          n-BuO  H     CH.sub.3                                                                              H     CH.sub.3                                                                          CH.sub.3                                          CH.sub.3                                                                              H     CH.sub.3 O                                                                            H     CH.sub.3                                                                          CH.sub.3                                          CH.sub.3                                                                              H     n-BuO  H     CH.sub.3                                                                          CH.sub.3                                          Cl     H     Cl     CH.sub.3 O                                                                           CH.sub.3                                                                          CH.sub.3                                          Cl     H     Cl     n-BuO CH.sub.3                                                                          CH.sub.3                                          CH.sub.3                                                                              CH.sub.3 O                                                                           H      H     CH.sub.3                                                                          CH.sub.3                                          CH.sub.3                                                                              n-BuO H      H     CH.sub.3                                                                          CH.sub.3                                          t-Bu   H     t-Bu   H     CH.sub.3                                                                          Et                                                t-Bu   H     t-Bu   H     Et CH.sub.3                                          CHCHCHCH     H      H     CH.sub.3                                                                          CH.sub.3                                                                          140-144(dec.)                                  H      H     CHCHCHCH     CH.sub.3                                                                          CH.sub.3                                                                          148-152(dec.)                                  __________________________________________________________________________

                  TABLE 6                                                          ______________________________________                                          ##STR17##                                                                     R.sup.11                                                                             R.sup.12                                                                               R.sup.13                                                                               R.sup.14                                                                             R.sup.10                                                                             melting point °C.                     ______________________________________                                         t-Bu  H       t-Bu    H     CH.sub.3                                           t-Bu  H       H       t-Bu  CH.sub.3                                           CH.sub.3                                                                             CH.sub.3                                                                               CH.sub.3                                                                               CH.sub.3                                                                             CH.sub.3                                           t-Bu  H       t-Bu    H     Et                                                 Cl    H       Cl      H     CH.sub.3                                           ______________________________________                                    

                                      TABLE 7                                      __________________________________________________________________________      ##STR18##                                                                     R.sup.11                                                                             R.sup.12                                                                             R.sup.13                                                                             R.sup.14                                                                             melting point °C.                               __________________________________________________________________________     t-Bu  H     t-Bu  H                                                            t-Bu  H     H     t-Bu                                                         CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3                                                                             CH.sub.3                                                     Cl    H     Cl    H                                                            Cl    CH.sub.3                                                                             CH.sub.3                                                                             H                                                            H     CH.sub.3                                                                             Cl    CH.sub.3                                                     __________________________________________________________________________

                  TABLE 8                                                          ______________________________________                                          ##STR19##                                                                     R.sup.11 R.sup.12 R.sup.13 R.sup.14                                                                              melting point °C.                     ______________________________________                                         t-Bu     H        t-Bu     H                                                   t-Bu     H        H        t-Bu                                                Cl       H        Cl       H                                                   Cl       CH.sub.3 CH.sub.3 H                                                   H        CH.sub.3 Cl       CH.sub.3                                            CH.sub.3 H        CH.sub.3 H                                                   ______________________________________                                    

FORMULATIONS

Useful formulations of the compounds of Formulae I and IX can be prepared in conventional ways. They include dusts, granules, pellets, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of them can be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositions are used primarily as concentrates which are to be diluted prior to ultimate use. The formulations, broadly, contain about 0.1% to 99% by weight of active ingredient(s) and at least one of (a) about 0.1% to 20% surfactant(s) and (b) about 1% to 99.9% solid or liquid diluent(s). More specifically, they will contain these ingredeints in the approximate proportions set forth in Table 5.

                  TABLE 9                                                          ______________________________________                                                        Weight Percent*                                                                Active            Surfac-                                                      Ingredient                                                                             Diluent(s)                                                                               tant(s)                                       ______________________________________                                         Wettable Powders 20-90      0-74     1-10                                      Oil Suspensions,  5-50     40-95     0-15                                      Solutions,                                                                     Emulsions                                                                      (including                                                                     Emulsifiable                                                                   Concentrates)                                                                  Aqueous Suspensions                                                                             10-50     40-84     1-20                                      Dusts             1-25     70-99     0-5                                       Granules and Pellets                                                                            0.1-95      5-99.9  0-15                                      High Strength Compositions                                                                      90-99      0-10     0-2                                       ______________________________________                                          *Active Ingredient plus at least one of Surfactant or a Diluent equals 10      weight percent.                                                          

Lower or higher levels of active ingredient can be present, depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation, or by tank mixing.

Some typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, N.J., but other solids, either mined or manufactured, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide", 2nd Ed., Interscience, N.Y., 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0° C. "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, N.J., as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, microbiological growth, etc.

The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending, and usually grinding, as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Pat. No. 3,060,084). Granules and pellets can be made by spraying the active material on preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration", Chemical Engineering, Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Engineer's Handbook", 4th Ed., McGraw-Hill, New York, 1963, pp. 8-59ff.

For further information regarding the art of formulation, see for example: J. E. Browning, "Agglomeration", Chemical Engineering, Dec. 4, 1967 pp. 147ff and "Perry's Chemical Engineer's Handbook", 4th. Edn., McGraw-Hill, New York, 1963, pp. 8-59ff.

For further information regarding the art of formulation, see for example:

J. B. Buchanan, U.S. Pat. No. 3,576,834, Apr. 27, 1971, Col. 5 Line 36 through Col. 7, Line 70 and Ex. 1-4, 17, 106, 123-140.

R. R. Shaffer, U.S. Pat. No. 3,560,616, Feb. 2, 1971, Col. 3, Line 48 through Col. 7, Line 26 and Examples 3-9, 11-18. E. Somers, "Formulation", Chapter 6 in Torgeson, "Fungicides", Vol. I, Academic Press, New York, 1967.

EXAMPLE 4

    ______________________________________                                         Wettable Powder                                                                ______________________________________                                         N-[[[N-[[N-[3,5-bis(1,1- 40%                                                   dimethylethyl)-4-oxo-2,5-                                                      cyclohexadien-1-ylidene-                                                       aminooxycarbonyl]-N-methyl-                                                    aminothio]]-N-methylamino-                                                     carbonyloxy]]]ethanimido-                                                      thioic acid, methyl ester                                                      Dioctyl sodium sulfosuccinate                                                                            1.5%                                                 Sodium ligninsulfonate    3%                                                   Low viscosity methyl cellulose                                                                           1.5%                                                 Attapulgite              54%                                                   ______________________________________                                    

The ingredients are thoroughly blended, passed through an air mill, to produce an average particle size under 15 microns, reblended, and sifted through a U.S.S.No. 50 sieve (0.3 mm opening) before packaging.

All compounds of the invention may be formulated in the same manner.

EXAMPLE 5

    ______________________________________                                         Solution                                                                       ______________________________________                                         N-[[[N-[[N-[3,5-bis(1,1-                                                                            30%                                                       dimethylethyl)-4-oxo-2,5-                                                      cyclohexadien-1-ylidene-                                                       aminooxycarbonyl]-N-methyl-                                                    amino]]-N-methylamino-                                                         carbonyloxy]]]ethanimido-                                                      thioic acid, methyl ester                                                      Dimethylformamide    70%                                                       ______________________________________                                    

The ingredients are combined and stirred to produce a solution, which can be used for low volume applications.

EXAMPLE 6

    ______________________________________                                         Dust                                                                           ______________________________________                                         N-[[[N-[[N-[3,5-bis(1,1-                                                                            10%                                                       dimethylethyl)-4-oxo-2,5-                                                      cyclohexadien-1-ylidene-                                                       aminooxycarbonyl]-N-methyl-                                                    amino]]-N-methylamino-                                                         carbonyloxy]]]ethanimido-                                                      thioic acid, methyl ester                                                      Attapulgite          10%                                                       Pyrophyllite         80%                                                       ______________________________________                                    

The active ingredient is blended with attapulgite and then passed through a hammer mill to produce particles substantially all below 200 microns. The ground concentrate is then blended with powdered pyrophyllite until homogeneous.

EXAMPLE 7

    ______________________________________                                         Aqueous Suspension                                                             ______________________________________                                         N-[[[N-[[N-[3,5-bis(1,1- 25%                                                   dimethylethyl)-4-oxo-2,5-                                                      cyclohexadien-1-ylidene-                                                       aminooxycarbonyl]-N-methyl-                                                    amino]]-N-methylamino-                                                         carbonyloxy]]]ethanimido-                                                      thioic acid, methyl ester                                                      Hydrated attapulgite      3%                                                   Crude calcium ligninsulfonate                                                                           10%                                                   Sodium dihydrogen phosphate                                                                              0.5%                                                 Water                    61.5%                                                 ______________________________________                                    

The ingredients are ground together in a ball or roller mill until the solid particles have been reduced to diameters under 10 microns.

EXAMPLE 8

    ______________________________________                                         Wettable Powder                                                                ______________________________________                                         N-[[[N-[[N-[3,5-bis(1,1-                                                                              50%                                                     dimethylethyl)-4-oxo-2,5-                                                      cyclohexadien-1-ylidene-                                                       aminooxycarbonyl]-N-methyl-                                                    amino]]-N-methylamino-                                                         carbonyloxy]]]ethanimido-                                                      thioic acid, methyl ester                                                      Sodium alkylnaphthalenesulfonate                                                                       2%                                                     Low viscosity methyl cellulose                                                                         2%                                                     Diatomaceous earth     46%                                                     ______________________________________                                    

The ingredients are blended, coarsely hammermilled and then air milled to produce particles of active essentially all below 10 microns in diameter. The product is reblended before packaging.

EXAMPLE 9

    ______________________________________                                         Granule                                                                        ______________________________________                                         Wettable powder of Example 8                                                                        10%                                                       Attapulgite granules 90%                                                       (U.S.S. # 20-40; 0.84-0.42 mm)                                                 ______________________________________                                    

A slurry of wettable powder containing 50% solids is sprayed on the surface of attapulgite granuels in a double-cone blender. The granules are dried and packaged.

USE

The compounds of this invention of Formulae I and IX have insecticidal activity on major agricultural, public health, and household pests.

The examples below demonstrate the control efficacy of these compounds.

These compounds have a wide spectrum of insecticidal activity, controlling economically significant pest species in the orders Lepidoptera, Homoptera, Diptera, and Coleoptera. More specifically, insects controlled by these compounds include, but are not limited to, the southern armyworm (Spodoptera eridania), bean aphid (Aphis fabae), housefly (Musca domestica), boll weevil (Anthonomus grandis grandis), and tobacco budworm (Heliothis virescens).

Control is achieved through application of one or more of the insecticidal compounds of this invention to the area to be protected, to the pests themselves, and/or the locus of infestation. The usual methods of application to agricultural crops, using compounds of this invention, are by foliar applications or applications to those plant parts which are to be protected. Applications, however, are not limited to these methods. The rate of application required for effective control is dependent upon both biological factors, e.g. the pest species, its life stage, size, and locations and upon non-biological factors, e.g. weather conditions (temperature, rainfall, humidity, etc.), time of year, application method, crop (plant growth habit and characteristics), and agronomic factors (crop spacing, soil type, etc.). In general, application rates of 0.07 to 8 kg/ha may be required for pest control in agriculture, the rates being dependent upon the above-listed biological and non-biological factors. However, rates of 0.14 to 2 kg/ha will, under normal circumstances, result in effective control. Rates of 0.28 to 1.5 kg/ha will normally be used in large scale field operations.

Compounds of this invention of Formulae I and IX can be mixed with insecticides, fungicides, nematicides, bactericides, acaricides, and/or other biologically active compounds, in order to achieve effective control with a minimum of input of material, time, and effort. The mixture ratio for each part by weight of compounds of this invention with the above-listed biologically active chemicals may vary from 0.20 to 5.00 parts by weight. The following list consists of a few select examples of chemicals presently employed in the above-listed control classes. The mixture composition, however, is not be be construed as being limited solely to the various possible combinations of those compounds.

Insecticides:

3-hydroxy-N-methylcrotonamide(dimethylphosphate)ester (Azodrin®) methylcarbamic acid, ester with 2,3-dihydro-2,2-dimethyl-7-benzofuranol (Furadan®)

-O[2,4,5-trichloro-α-(chloromethyl)benzyl]phosphoric acid, O',O'-dimethyl, ester (Gardona®)

2-mercaptosuccinic acid, diethyl ester, S-ester with thionophosphoric acid, dimethyl ester (Malathion®)

phosphorothioic acid, O,O-dimethyl, O-p-nitrophenyl ester (methyl parathion)

methylcarbamic acid, ester with α-naphthol (Sevin®)

methyl O-methylcarbamoyl)thiolacetohydroxamate (methomyl)

N'-(4-chloro-o-tolyl)-N,N-dimethylformamidine (Galecron®)

O,O-diethyl-O-(2-isopropyl-4-methyl-6-pyrimidylphosphorothioate (Diazinon®)

octachlorocamphene (toxaphene)

O-ethyl O-p-nitrophenyl phenylphosphonothioate (EPN)

cyano(3-phenoxyphenyl)-methyl-4-chloro-α-(1-methylethyl)-benzeneacetate (Pydrin®) (3-phenoxyphenyl)methyl(±)-cis,trans-3-(2,2,-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate (Ambush®)

O-ethyl-S-(p-chlorophenyl)ethylphosphonodithioate (Curacron®)

phosphorothiolothionic acid, O-ethyl-O-[ 4-(methylthio)phenyl]-S-n-propyl ester (Bolstar®)

Fungicides:

methyl 2-benzimidazolecarbamate (carbendazim)

tetramethyl thiuram disulfide (thiram)

n-dodecylguanidine acetate (dodine)

manganese ethylenebisdithiocarbamate (maneb)

1,4-dichloro-2,5-dimethoxybenzene (chloroneb)

methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate (benomyl)

2-cyano-N-ethylcarbamoyl-2-methoxyiminoacetamide (Curzate®)

N-trichloromethylthiotetrahydrophthalimide (captan)

N-trichloromethylthiophthalimide (folpet)

Nematicides:

S-methyl 1-(dimethylcarbamoyl)-N-(methylcarbamoyloxy)thioformimidate (oxamyl)

S-methyl 1-carbamoyl-N-(methylcarbamoyloxy)thioformimidate

N-isopropylphosphoramidic acid, O-ethyl-O' -[4-(methylthio)-m-tolyl]diester (Nemacur®)

Bactericides:

tribasic copper sulfate

streptomycin sulfate

Acaricides:

senecioic acid, ester with 2-sec-butyl-4,6-dinitrophenol (Morocide®)

6-methyl-1,3-dithiolo[2,3-B]quinonolin-2-one, (Morestan®) ethyl 4,4'-dichlorobenzilate (Chlorobenzilate®)

1,1-bis(p-chlorophenyl)-2,2,2-trichloroethanol (Kelthane®) bis(pentochloro-2,4-cyclopentadien-lyl) (Pentac®) tricyclohexyl trihydroxide (Plictran®)

EXAMPLE 10

The foliage only of red kidney bean plants in the two-leaf stage were sprayed to run-off with dispersions of compounds of this invention at various concentrations. Dispersions were prepared by dissolving appropriately weighed quantities of the active ingredient in 10 ml of acetone and diluting to 100 ml with water containing a surface active agent (Duponol® L-144 WDG) at 1:3000. After drying, leaves were excised and placed in covered 10 cm petri dishes along with moist filter paper to keep them fresh. Ten southern armyworm larvae were placed in each dish. Tests were run in duplicate. The units were kept in a room maintained at 25°±2° C., 53±5% RH. Results were recorded at the end of 2 days.

                  TABLE 10                                                         ______________________________________                                                         % a.i..sup.1 Spray                                             Compound        Concentration % Mortality                                      ______________________________________                                         Methyl N-[[[N-[[N-[3,5-                                                        bis(1,1-dimethylethyl)-                                                                        .005          100                                              4-oxo-2,5-cyclohexadien-                                                                       .0025          90                                              1-ylideneaminooxycarbonyl]-                                                    N-methylaminothio]]-N-                                                         methylaminocarbonyloxy]]]-                                                     ethanamidothioate                                                              ______________________________________                                          .sup.1 a.i. means active ingredient                                      

EXAMPLE 11

The foliage of red kidney bean plants in the two-leaf stage was sprayed to run-off with dispersions of compounds of this invention at various concentrations. Dispersions were prepared by dissolving appropriately weighed quantities of the active ingredient in 10 ml of acetone and diluting to 100 ml with water containing a surface active agent (Duponol® L-144 WDG) at 1:3000. After drying, plants were placed under artificial light in a room maintained at 25°±2° C., 54±5% RH. After the designated period, leaves were excised and placed in covered 10 cm petri dishes along with moist filter paper to keep them fresh. Ten southern armyworm larvae were placed in each dish. These were run in duplicate. The units kept in a room maintained at 25°±2° C., 54±5% RH. Results were recorded 2 days after larvae were placed on the treated foliage.

                  TABLE 11                                                         ______________________________________                                                       % a.i.  % Mortality (2 days)                                                     Spray Con-                                                                               2 Days    7 Days                                     Compound        centration                                                                               Residual  Residual                                   ______________________________________                                         Methyl N-[[[N-[[N-[3,5-                                                        bis(1,1-dimethylethyl)-                                                                        0.01      100       95                                         4-oxo-2,5-cyclohexadien-                                                                       0.005      80       75                                         1-ylideneaminooxycarbonyl]-                                                    N-methylaminothio]]-N-                                                         methylaminocarbonyloxy]]]-                                                     ethanamidothioate                                                              ______________________________________                                    

EXAMPLE 12

Potted Stoneville 213 cotton plants approximately 25 cm high having 3-4 true leaves were sprayed to run-off with aqueous dispersions of compounds of this invention at 500 ppm. The sprays contained a surface active agent (Duponol® L-144 WDG) at a concentration of 1:3000. Another set of plants was similarly treated with methomyl. After drying, the plants were set out in the greenhouse and held for observation. Results were recorded after 5 days.

                  TABLE 12                                                         ______________________________________                                         Compound (500 ppm a.i.).sup.1                                                                     Rating.sup.2 (5 Days)                                       ______________________________________                                         Methyl N-[[[N-[[N-[3,5-                                                        bis(1,1-dimethylethyl)-                                                        4-oxo-2,5-cyclohexadien-                                                                          0                                                           1-ylideneaminooxycarbonyl]-                                                    N-methylaminothio]]-N-                                                         methylaminocarbonyloxy]]]-                                                     ethanamidothioate                                                              Methyl O-(methylcarbamoyl)-                                                    thiolacetohydroxamate                                                                             3R                                                          (methomyl)                                                                     Untreated Control  0                                                           ______________________________________                                          .sup.1 a.i.  active ingredient                                                 .sup.2 "R" denotes typical methomyl effective, i.e., reddening of older        leaves, slight puckering and black stippling of younger leaves. Rating is      on the basis of 0-10 with 0 indicating no effect and 10 indicating total       leaf area involvement.                                                   

EXAMPLE 13

The foliage only of red kidney bean plants in the two-leaf stage were sprayed to run-off with dispersions of compounds of this invention at various concentrations. Dispersions were prepared by dissolving appropriately weighed quantities of the active ingredient in 10 ml of acetone and diluting to 100 ml with water containing a surface active agent (Duponol® L-144 WDG) at 1:3000. After drying, leaves were excised and placed in covered 10 cm petri dishes along with moist filter paper to keep them fresh. Ten southern armyworm larvae were placed in each dish. Tests were run in duplicate. The units were kept in a room maintained at 25°±2° C., 55±5% RH. Results were recorded at the end of 2 days.

                  TABLE 13                                                         ______________________________________                                                           % Mortality (2 days)                                                             0.01%     0.005%                                           Compound            A.I.      A.I.                                             ______________________________________                                         Methyl N-[[[N-[[N-[3,5-bis-   100                                              (1,1-dimethylethyl)-4-oxo-                                                                         --                                                         2,5-cyclohexadien-1-yl-                                                        ideneaminooxycarbonyl]-N-                                                      methylaminothio]]-N-methyl-                                                    aminocarbonyloxo]]]-                                                           ethanamidothioate             --                                               Methyl N-[N-[N-(3,5-dimethyl-                                                                      100                                                        4-oxo-2,5-cyclohexadien-1-                                                     ylideneaminooxycarbonyl)-N-                                                    methylaminothio]-N-methyl-                                                     aminocarbonyloxy]ethanimido-                                                   thioate                                                                        Methyl N-[N-methyl-N-[N-                                                                            95       --                                               methyl-N-[2-methyl-5-(1-                                                       methylethyl)-4-oxo-2,5-                                                        cyclohexadien-1-ylidene-                                                       aminooxycarbonyl]aminothio]-                                                   aminocarbonyloxy]ethanimido-                                                   thioate                                                                        Methyl N-[N-[N-[ 3,5-bis-(1-                                                                       --         90                                              methylethyl)-4-oxo-2,5-cyclo-                                                  hexadien-1-ylideneaminooxy-                                                    carbonyl]-N-methylaminothio]-                                                  N-methylcarbonyloxy]-                                                          ethanimidothioate                                                              Methyl N-[N-[N-[3,5-bis(1-                                                                         100       --                                               methylethyl-4-oxo-2,5-cyclo-                                                   hexadien-1-ylideneaminooxy-                                                    carbonyl]-N-methylaminothio]-                                                  N-methylcarbonyloxy]-                                                          ethanimidothioage                                                              Methyl N-[N-[N-[2,5-bis(1,1-                                                                       --        100                                              dimethylethyl)-4-oxo-2,5-                                                      cyclohexadien-1-ylideneamino-                                                  oxycarbonyl]-N-methylamino-                                                    thio]-N-methylaminocarbonyl-                                                   oxy]ethanimidothioate                                                          Methyl N-[N-[N-[5-(1,1-di-                                                                         --         95                                              methylethyl)-2-methyl-4-oxo-                                                   2,5-cyclohexadien-1-ylidene-                                                   aminooxycarbonyl]-N-methyl-                                                    aminothio]-N-methylamino-                                                      carbonyloxy]ethanimidothioate                                                  Methyl N-[N-[N-[3,5-bis(1,1-                                                                       --         95                                              dimethylethyl)-6-oxo-2,4-                                                      cyclohexadien-1-ylidene-                                                       aminooxycarbonyl-N-methyl-                                                     aminothio]-N-methylamino-                                                      carbonyloxy]ethanimidothioate                                                  Methyl N-[N-methyl-N-[N-methyl-                                                                    --        100                                              N-(2,3,5,6-tetramethyl-4-oxo-                                                  2,5-cyclohexadien-1-ylidene-                                                   aminooxycarbonyl]aminothio]-                                                   aminocarbonyloxy]ethanimido-                                                   thioate                                                                        Methyl N-[N-methyl-N-[N-methyl-                                                N-(4-oxo-2,5-cyclohexadien-1-                                                                      --        100                                              ylideneaminooxycarbonyl)-                                                      aminothio]aminocarbonyloxy]                                                    ethanimidothioate                                                              Methyl N-[N-[N-(3,5-dichloro-4-                                                                    100       --                                               oxo-2,5-cyclohexadien-1-yl-                                                    ideneaminooxycarbonyl)-N-                                                      methylaminothio]-N-methyl-                                                     aminocarbonyloxy]ethanimido-                                                   thioate                                                                        Methyl N-[N-[N-(2,5-dimethyl-                                                                      100       --                                               4-oxo-2,5-cyclohexadien-1-yl-                                                  ideneaminooxycarbonyl)-N-                                                      methylaminothioate]-N-methyl-                                                  aminocarbonyloxy]ethanimido-                                                   thioate                                                                        ______________________________________                                    

EXAMPLE 14

Tobacco budworm, Heliothis virescens, larvae were treated topically with compounds of this invention. One microliter of each concentration used was applied to the dorsoprothoracic area of each larva tested. The stock solutions were prepared by dissolving appropriately weighed quantities of active ingredient in predetermined quantities of acetone. Further diluting with acetone yielded the desired conentrations. Larvae were treated in the individual 1 oz. cups in which they were reared on artificial diet. Fifteen larvae were treated with the desired concentration and kept in a growth room at 26°±0.5° C. and 50-60% RH. Mortality readings were taken at 48 hours.

                  TABLE 14                                                         ______________________________________                                                              % Mortality (48 hours)                                    Compound             0.25 μ g/larva                                         ______________________________________                                         Methyl N-[[[N-[[N-[3,5-bis(1,1-                                                                     83                                                        dimet-ylethyl)-4-oxo-2,5-cyclo-                                                hexadien-1-ylideneaminooxy-                                                    carbonyl]-N-methylaminothio]]-                                                 N-methylaminocarbonyloxy]]]-                                                   ethanamidothioate                                                              Methyl N-[N-[N-(3,5-dimethyl-4-                                                                     87                                                        oxo-2,5-cyclohexadien-1-yl-                                                    ideneaminooxycarbonyl)-N-methyl-                                               aminothio]-N-methylaminocar-                                                   bonyloxy]ethanimidothioate                                                     ______________________________________                                    

EXAMPLE 15

Stems of nasturium leaves infested with black bean aphid, Aphis fabae, were placed in individual vials containing aqueous dispersions of compounds of this invention at various concentrations. Dispersions were prepared by dissolving appropriately weighed quantities of the active ingredient in 10 ml of acetone and diluting to 100 ml with water containing a surface active agent (Duponol® 1-144 WDG) at 1:3000. The units were kept in a room maintained at 25°±2° C., 55±5% RH. Results were recorded at the end of 1 day.

                  TABLE 15                                                         ______________________________________                                                           % Mortality (1 day)                                                            % a.i. Spray concentration                                   Compound            0.005     0.0025                                           ______________________________________                                         Methyl N-[[[N-[[N-[3,5-bis(1,1-                                                                    84        --                                               dimethylethyl)-4-oxo-2,5-cylco-                                                hexadien-1-ylideneaminooxy-                                                    carbonyl]-N-methylaminothio]  ]-                                               N-methylaminocarbonyloxy]]-                                                    ethanamidothioate                                                              Methyl N-[N-methyl-N-[N-methyl-                                                                    --        100                                              N-[2-methyl-5-(1-methylethyl)-                                                 4-oxo-2,5-cyclohexadien-1-yl-                                                  ideneaminooxycarbonyl]amino-                                                   thio]aminocarbonyloxy]-                                                        ethanimidothioate                                                              Methyl N-[N-[N-[3,5-bis(1-                                                                         93        --                                               methylpropyl)-4-oxo-2,5-                                                       cyclohexadien-1-ylideneamino-                                                  oxycarbonyl]-N-methylamino-                                                    thio]-N-methylaminocarbonyl-                                                   oxy]ethanimidothioate                                                          ______________________________________                                    

EXAMPLE 16

Nasturtium leaves, infested with black bean aphid, Aphis fabae, were placed in individual vials of water. The leaves were sprayed to runoff with dispersions of compounds of this invention at various concentrations. Dispersions were prepared by dissolving appropriately weighed quantities of the active ingredient in 10 ml of acetone and diluting to 100 ml with water containing a surface active agent (Duponol® L-144 WDG) at 1:3000. The units were kept in a room maintained at 25°±2° C., 55±5% RH. Results were recorded at the end of 1 day.

                  TABLE 16                                                         ______________________________________                                                           % Mortality (1 day)                                                            % A.I. Concentration                                         Compound            0.005     0.0025                                           ______________________________________                                         Methyl N-[N-methyl-N-[N-methyl-                                                                    --        100                                              N-[2-methyl-5-(1-methylethyl)-                                                 4-oxo-2,5-cyclohexadien-1-yl-                                                  ideneaminooxycarbonyl]amino-                                                   thio]aminocarbonyloxy]-                                                        ethanimidothioate                                                              Methyl N-[N-[N-[3,5-bis(1-                                                                         99        --                                               methylpropyl)-4-oxo-2,5-                                                       cyclohexadien-1-ylidene-                                                       aminooxycarbonyl]-N-methyl-                                                    aminothio]-N-methylamino-                                                      carbonyloxy]ethanimidothioate                                                  ______________________________________                                     

What is claimed is:
 1. A compound of the formula ##STR20## R¹, R², R³, and R⁴ are independently H, F, Cl, Br, NO₂, CN, CF₃, C₁ -C₁₂ alkyl, C₁ -C₄ alkoxy, or COR⁵ ;R⁵ is OR⁶ or NR⁷ R⁸ ; R⁶ is C₁ -C₄ alkyl; R⁷ is C₁ -C₄ alkyl or methoxy; R⁸ is C₁ -C₄ alkyl; R⁹ and R¹⁰ are independently methyl or ethyl; or R¹ and R² are taken together to form

    --CH═CH--CH═CH--;

provided that: (1) The total of R⁹ and R¹⁰ is not greater than three carbon atoms; (2) Only one of R¹, R², R³ and R⁴ can be CN, NO₂, COR⁵, or CF₃ ; (3) If R² and R⁴ are both alkyl, then R² and R⁴ are independently CH₃ or CH₂ CH₃ ; (4) If any two of R¹, R², R³, and R⁴ are independently halogen or alkoxy, then the other two are independently hydrogen or CH₃ ; (5) The total number of carbons R¹ to R⁴ is not greater than 26; (6) If R¹ and R² are both alkyl, then R² must be CH₃ or CH₂ CH₃ ; (7) If R³ and R⁴ are both alkyl, then R⁴ must be CH₃ or CH₂ CH₃.
 2. A compound of the Formula ##STR21## R⁹ and R¹⁰ are independently methyl or ethyl; R¹¹, R¹², R¹³ and R¹⁴ are independently, H, C₁ -C₁₂ alkyl, C₁ -C₄ alkoxy, Cl or Br; oreither R¹¹ and R¹² or R¹³ and R¹⁴ are taken together to form --Ch═CH--CH═CH--;provided that (1) the total of R⁹ and R¹⁰ is not greater than three carbon atoms; (2) if three or more of R¹¹, R¹², R¹³ and R¹⁴ are other than H, then any of R¹¹, R¹², R¹³ and R¹⁴ which is not H, is selected from CH₃ or Cl, except that if R¹¹ and R¹² or R¹³ and R¹⁴ form the bridge --CH═CH--CH═CH--, then the remaining R¹¹ to R¹⁴ groups are chosen from all definitions of R¹¹ to R¹⁴ ; (3) if any of R¹¹, R¹², R¹³ and R¹⁴ is secondary alkyl, tertiary alkyl or tertiary alkoxy, the adjacent group which is at least one of R¹¹, R¹², R¹³ or R¹⁴ must be selected from H, CH₃ or CH₂ CH₃ ; (4) the total number of carbons of R¹¹ to R¹⁴ is not greater than
 16. 3. The compound of claim 1 whereR¹ and R⁴ are independently H, Cl, F, C₁ -C₅ alkyl, C₁ -C₃ alkoxy, or CO₂ R₆ where R⁶ is C₁ -C₄ alkyl; and R¹¹ to R¹⁴ are independently H, Cl, C₁ -C₅ alkyl and C₁ -C₃ alkoxy.
 4. The compound of claim 3 where R⁹ and R¹⁰ are CH₃.
 5. The compound of claim 4 whereR² and R⁴ are H, R¹ and R³ are independently C₁ -C₅ alkyl, R¹² and R¹⁴ are H, and R¹¹ and R¹³ are independently C₁ -C₅ alkyl.
 6. The compound of claim 2 whereR¹ and R⁴ are independently H, Cl, F, C₁ -C₅ alkyl, C₁ -C₃ alkoxy, or CO₂ R₆ where R⁶ is C₁ -C₄ alkyl; and R¹¹ to R¹⁴ are independently H, Cl, C₁ -C₅ alkyl and C₁ -C₃ alkoxy.
 7. The compound of claim 6 where R⁹ and R¹⁰ are CH₃.
 8. The compound of claim 7 whereR² and R⁴ are H, R¹ and R³ are independently C₁ -C₃ alkyl, R¹² and R¹⁴ are H, and R¹¹ and R¹³ are independently C₁ -C₅ alkyl.
 9. The compound of claim 1 which is N-[[[N-[[N-[3,5-bis(1,1-dimethylethyl)-4-oxo-2,5-cyclohexadien-1-ylideneaminooxycarbonyl]-N-methylaminothio]]-N-methylaminocarbonyloxy]]]ethanimidothioic acid, methyl ester.
 10. The compound of claim 1 which is N-[N-[N-(3,5-dimethyl-4-oxo-2,5-cyclohexadien-1-ylideneaminooxycarbonyl)-N-methylaminothio]-N-methylaminocarbonyloxy]ethanimidothioic acid, methyl ester.
 11. The compound of claim 1 which is N-[N-methyl-N-[N-methyl-N-[2-methyl-5-(1-methylethyl)-4-oxo-2,5-cyclohexadien-1-ylideneaminooxycarbonyl]aminothio]aminocarbonyloxy]ethanimidothioic acid, methyl ester.
 12. The compound of claim 1 which is N-[N-[N-[3,5-bis(1-methylpropyl)-4-oxo-2,5-cyclohexadien-lylideneaminooxycarbonyl]-N-methylaminothio]-N-methylaminocarbonyloxy]ethanimidothioic acid, methyl ester.
 13. The compound of claim 1 which is N-[N-[N-[3,5-bis(1-methylethyl)-4-oxo-2,5-cyclohexadien-lylideneaminooxycarbonyl]-N-methylaminothio]-N-methylcarbonyloxy]ethanimidothioic acid, methyl ester.
 14. The compound of claim 2 which ismethyl N-[N-[N-[[3,5-bis(1,1-dimethylethyl)-6-oxo-2,4-cyclohexadien-1-ylidene]aminoxycarbonyl]-N-methylaminothio]-N-methylaminocarbonyloxy]ethanimidothioate
 15. The compound of claim 1 which ismethyl N-[N-[N-[(3-dodecyl-1,4-dihydro-4-oxo-1-naphthalenylidene)aminooxycarbonyl]-N-methylaminothio]-N-methylaminocarbonyloxy]ethanimidothioate.
 16. The compound of claim 2 which ismethyl N-[N-[N-[(1,2-dihydro-1-oxo-2-naphthalenylidene)aminooxycarbonyl]-N-methylaminothio]-N-methylaminocarbonyloxy]ethanimidothioate.
 17. The compound of claim 1 which ismethyl N-[N-[N-[(1,4-dihydro-3-methyl-4-oxo-1-naphthalenylidene)aminooxycarbonyl]-N-methylaminothio]-N-methylaminocarbonyloxy]-ethanimidothioate.
 18. An agricultural composition for insecticidal use consisting essentially of a surfactant, diluent or combinations thereof and a compound of claim
 1. 19. An agricultural composition for insecticidal use consisting essentially of a surfactant, diluent or combinations thereof and a compound of claim
 2. 20. An agricultural composition for insecticidal use consisting essentially of a surfactant, diluent or combinations thereof and a compound of claim
 3. 21. An agricultural composition for insecticidal use consisting essentially of a surfactant, diluent or combinations thereof and a compound of claim
 4. 22. An agricultural composition for insecticidal use consisting essentially of a surfactant, diluent or combinations thereof and a compound of claim
 5. 23. An agricultural composition for insecticidal use consisting essentially of a surfactant, diluent or combinations thereof and a compound of claim
 6. 24. An agricultural composition for insecticidal use consisting essentially of a surfactant, diluent or combinations thereof and a compound of claim
 7. 25. An agricultural composition for insecticidal use consisting essentially of a surfactant, diluent or combinations thereof and a compound of claim
 8. 26. An agricultural composition for insecticidal use consisting essentially of a surfactant, diluent or combinations thereof and a compound of claim
 9. 27. An agricultural composition for insecticidal use consisting essentially of a surfactant, diluent or combinations thereof and the compound of claim
 10. 28. An agricultural composition for insecticidal use consisting essentially of a surfactant, diluent or combinations thereof and the compound of claim
 11. 29. An agricultural composition for insecticidal use consisting essentially of a surfactant, diluent or combinations thereof and the compound of claim
 12. 30. An agricultural composition for insecticidal use consisting essentially of a surfactant, diluent or combinations thereof and the compound of claim
 13. 31. An agricultural composition for insecticidal use consisting essentially of a surfactant, diluent or combinations thereof and the compound of claim
 14. 32. An agricultural composition for insecticidal use consisting essentially of a surfactant, diluent or combinations thereof and the compound of claim
 15. 33. An agricultural composition for insecticidal use consisting essentially of a surfactant, diluent or combinations thereof and the compound of claim
 16. 34. An agricultural composition for insecticidal use consisting essentially of a surfactant, diluent or combinations thereof and the compound of claim
 17. 35. A method for control of insects which comprises applying to a locus to be protected an insecticidally effective amount of a compound of claim
 1. 36. A method for control of insects which comprises applying to a locus to be protected an insecticidally effective amount of a compound of claim
 2. 37. A method for control of insects which comprises applying to a locus to be protected an insecticidally effective amount of a compound of claim
 3. 38. A method for control of insects which comprises applying to a locus to be protected an insecticidally effective amount of a compound of claim
 4. 39. A method for control of insects which comprises applying to a locus to be protected an insecticidally effective amount of a compound of of claim
 5. 40. A method for control of insects which comprises applying to a locus to be protected an insecticidally effective amount of a compound of of claim
 6. 41. A method for control of insects which comprises applying to a locus to be protected an insecticidally effective amount of a compound of of claim
 7. 42. A method for control of insects which comprises applying to a locus to be protected an insecticidally effective amount of a compound of of claim
 8. 43. A method for control of insects which comprises applying to a locus to be protected an insecticidally effective amount of a compound of of claim
 9. 44. A method for control of insects which comprises applying to a locus to be protected an insecticidally effective amount of the compound of claim
 10. 45. A method for control of insects which comprises applying to a locus to be protected an insecticidally effective amount of the compound of claim
 11. 46. A method for control of insects which comprises applying to a locus to be protected an insecticidally effective amount of the compound of claim
 12. 47. A method for control of insects which comprises applying to a locus to be protected an insecticidally effective amount of the compound of claim
 13. 48. A method for control of insects which comprises applying to a locus to be protected an insecticidally effective amount of the compound of claim
 14. 49. A method for control of insects which comprises applying to a locus to be protected an insecticidally effective amount of the compound of claim
 15. 50. A method for control of insects which comprises applying to a locus to be protected an insecticidally effective amount of the compound of claim
 16. 51. A method for control of insects which comprises applying to a locus to be protected an insecticidally effective amount of the compound of claim
 17. 52. A compound of the formula ##STR22## R¹, R², R³, and R⁴ are independently H, F, Cl, Br, NO₂, CN, CF₃, C₁ -C₁₂ alkyl, C₁ -C₄ alkoxy, or COR⁵ ;R⁵ is OR⁶ or NR⁷ R⁸ ; R⁶ is C₁ -C₄ alkyl; R⁷ is C₁ -C₄ alkyl or methoxy; R⁸ is C₁ -C₄ alkyl; or R¹ and R² are taken together to form

    --CH═CH--CH═CH--;

R¹¹, R¹², R¹³ and R¹⁴ are independently, H, C₁ -C₁₂ alkyl, C₁ -C₄ alkoxy, Cl or Br; or either R¹¹ and R¹² or R¹³ and R¹⁴ are taken together to form --CH═CH--CH═CH--;provided that: (1) Only one of R¹, R², R³ and R⁴ can be CN, NO₂, COR⁵, or CF₃ ; (2) If R² and R⁴ are both alkyl, then R² and R⁴ are independently CH₃ or CH₂ CH₃ ; (3) If any two of R¹, R², R³, and R⁴ are independently halogen or alkoxy, then the other two are independently hydrogen or CH₃ ; (4) The total number of carbons R¹ to R⁴ is not greater than 26; (5) If R¹ and R² are both alkyl, then R² must be CH₃ or CH₂ CH₃ ; (6) If R³ and R⁴ are both alkyl, then R⁴ must be CH₃ or CH₂ CH₃ ; (7) if three or more of R¹¹, R¹², R¹³ and R¹⁴ are other than H, then any of R¹¹, R¹², R¹³ and R¹⁴ which is not H is selected from CH₃ or Cl, except that if R¹¹ and R¹² or R¹³ and R¹⁴ form the bridge --CH═CH--CH═CH--, then the remaining R¹¹ to R¹⁴ groups are chosen from all definitions of R¹¹ to R¹⁴ ; (8) if any of R¹¹, R¹², R¹³ and R¹⁴ is secondary alkyl, tertiary alkyl or tertiary alkoxy, the adjacent group which is at least one of R¹¹, R¹², R¹³ or R¹⁴ must be selected from H, CH₃ or CH₂ CH₃ ; (9) the total number of carbons of R¹¹ to R¹⁴ is not greater than
 16. 